Azo pigments containing a 4-carboxamido phenomorpholene-(3) group

ABSTRACT

Compounds of the formula R1-N N-R2-CONH-R3 in which R1 and R3 each represents an aryl or a heterocyclic residue, at least one of the residues R1 and R3 being a phenomorpholone-(3) residue, and R2 represents a hydroxynaphthalene residue in which the azo, hydroxy and carboxylic acid amide groups are in 1,2,3-position or the residue of an enolizable or enolized ketomethylene compound are valuable pigments which are useful for coloring plastics and lacquers in fast yellow-to-red shades of excellent fastness properties.

United States Patent Inventor Rudolf Mory Dornach, Switzerland Appl. No. 762,163 Filed Sept. 24, 1968 Patented Sept. 28, 1971 Assignee Ciba-Geigy A.G.

Basle, Switzerland Priority Oct. 10, 1967, July 25, 1968 Switzerland 14143/67 and 11205/68 AZO PIGMENTS CONTAINING A 4- CARBOXAMIDO PHENOMORPHOLENE-(3) GROUP 14 Claims, No Drawings US. Cl 260/152, 8/4, 8/41 R, 8/41 B, 8/41 C, 8/41 D, 8/50,106/23, 106/288, 117/138.8 R, l17/138.8 B, 117/1388 D,

117/1388 E, 117/1388 F, 117/143 F, 117/144, 260/37 R, 260/37 N, 260/40 R, 260/41 C, 260/157, 260/247.5 R, 260/558 D, 260/559 A,

Int. Cl C09b29/36, C09b 35/18, D06p 1/04 Field of Search 260/ 152,

[56] References Cited UNITED STATES PATENTS 1,567,731 12/1925 Gunther 260/152 2,364,351 12/1944 Dickey 260/154 2,883,374 4/1959 Enders 260/152 X 2,908,678 10/1959 Goebel et al 260/154 3,043,827 7/1962 Straley et al. 260/152 3,118,870 H1964 Dietz et a1 260/154 3,124,565 3/1964 Schilling et a1. 260/157 Primary Examiner- Floyd D. Higel Attorneys-Harry Goldsmith, Joseph G. Kolodny, Bryant W.

Brennan and Edward J. Sites AZO PIGMENTS CONTAINING A 4-CARBOXAMIDO PHENOMORPHOLENE-(3) GROUP R1N=N R: l 5 with an amine of the formula or (b) coupling a diazo or diazoamino compound of an amine of the formula R,Nl-l with a coupling component of the formula the components being so selected that one of the residues R or R contains a phenomorpholone residue.

Since the products of the invention are pigments, they must not contain groups imparting solubility in water, especially acidic groups imparting solubility in water, for example, sulfonic acid groups or carboxylic acid groups.

Products that are of special interest are those of the formula in which R represents a benzene residue, R represents a phenomorpholone-(Ii) residue and Y represents a hydrogen atom or an alkoxy or cyano group. These pigments preferably correspond to the formula l l@ N CONH m which X represents a halogen atom or an alkyl, alkoxy, phenoxy, nitro or carboxylic acid ester group, U represents a hydrogen or a halogen atom or a nitro or trifluoromethyl group, V represents a hydrogen or a halogen atom or a trifluoromethyl or carboxylic acid amide group, Z represents a hydrogen or a halogen atom or an alkyl group and Y has the meaning give above, X, Y, Z, U and V may be further defined as X being hydrogen, chlorine, lower alkyl, lower alkoxy. phenoxy, nitro or lower carbalkoxy, Y being hydrogen, bromine, methoxy or cyano; 2 being hydrogen, chlorine, lower alkyl or lower alkoxy; U being hydrogen, chlorine, nitro or trifluoromethyl; and V being hydrogen, chlorine, trifluoromethyl or carboxylic amide group selected from the group consisting of -CONH-aryl, wherein aryl is benzene, naphthalene or para-diphenyl or benzene, naphtalene or paradiphenyl substituted with chloro, lower alkyl, lower alkoxy or trifluoromethyl; and a phenomorpholone-(S) group of the formula Co a Z H wherein Z is selected from the group consisting of hydrogen, chloro, lower alkyl or lower alkoxy.

Pigments having specially good properties are those cor responding to the formula I Y CONHR- in which X represents a halogen atom or an alkyl or alkoxy group, R and R, each represents a benzene or a phenomorpholone-(3) residue, at least one of the residues R and R, representing a phenomorpholone-(El) residue, and Y and Z have the meanings given above.

Also of interest are pigments of the formula N-Ri H N l Y l COC-l with an aminophenomorpholone.

The azo dyestuff carboxylic acids, from which the acid chlorides of the formula (9) are prepared, may be obtained by coupling a diazo compound of an amine of the formula R,- Nl-l with a 2,3-hydroxynaphthoic acid of the formula which is substituted at 6-position, if desired, with a halogen atom or an alkoxy or cyano group,

The following are given as examples of diazotizable amines of the formula R Nl-l aniline, and especially halogenated anilines, for example, 2- nitroaniline, 3- or 433,4-dichloroaniline, 2,3-dichloroaniline, 2,4-dichloroaniline, 2,5-dichloroaniline, 2,6-dichloraniline, 2,4,5-trichloroaniline, 2,4,6-trichloroaniline, 2-, 3- or 4- bromoaniline, 2,4-dibromoaniline, 2,5-dibromoaniline, 2- methyl-S-chloroaniline, 2-methyl-4-chloroaniline, 2-methyl-3- chloroaniline, Z-chloro-Strifluoromethylaniline also nitroanilines, for example, 2-, 3- and 4-nitroaniline, 4-chloro- 2-nitroaniline, 2-chloro-4-nitr0aniline, 4-methyl-3- nitroaniline, 2,4-dimethyl-3-nitroaniline, 2-rnethyl-5- nitroaniline, 2-methyl-4-nitroaniline, and also alkoxy and phenoxy anilines, for example, 2- and 4-methoxyaniline, Z-and 4-ethoxyaniline, 3-chloro-4-methoxyaniline, 2methoxy-5- nitroaniline, Z-methoxy-S-chloroaniline, Z-methoxy- Strifluoromethylaniline, 2-amino- 4-trifluoromethyl-4'- chlorodiphenylether, 2-nitro-4-ethoxyaniline, 2-methoxy-4- chloro-S-methylaniline, 2-amino-4 -chlorodiphenylether, 2- amino-Z,4-dichlorodiphenylether, 2-amino-4,4'- dichlorodiphenylether, 2-amin0-4 trifluoromethyldiphenylether, 4-amino-2-trifluoromethyldiphenylether, 4-amino-2- trifluoromethyl-2',4'-dichlorodiphenylether, l-amino-Z-carboxylic acid methylester and also 1-amino-2-chloro-5-carboxylic acid methylester, 2-amino-5-nitrobenzoic acid methylester, 4-amino-3nitrobenzotrifluoride, Z-amino-S- nitrobenzotrifluoride, l-amino-2-chlorobenzene-5-carboxylic acid methylamide, 2,5-dimethoxy-4-benzoylaminoaniline, 2,5dimethyl-4benzoylaminoaniline, 2-chloro-5-methoxy-4- benzoylaminoaniline, 2-methoxy-5-methyl-4- benzoylaminoaniline, but especially 4-methyl-3-arninobenzoic acid amide, 4-methyl-3-aminobenzoic acid anilide, 4-methyl- 3-amin0benzoic acid-2'-chloro-5'4rifluoromethylanilide, 4- chloro-3-aminobenzoic acid-3 ,5 '-bis-trifluoromethylanilide, 4-chloro3--aminobenzoic acid-2' ,4 ,5-trichloroanilide, 2 ,4- dichloro-S-aminobenzoic acid-2' ,5 '-dichloroanilide, 2 ,4- dichloro-S aminobenzoic acid-2',4-dichloroanilide, 2,4- dichloro-S-aminobenzoic acid-3'-trifluorometl'iylanilide, 2,4- dichloro-S-aminobenzoic acid-3-chloroanilide, 2,4-dichloro- S-aminobenzoic acid amide, 5-amino-4-methoxy-2- chlorobenzoic acid-3'-trifluoromethylanilide, 4-methyl-3- aminobenzoic acid-2' ,5 '-dichloroanilide, 4-mcthyl-3- aminobenzoic acid-3-trifluoromethylanilide, 4-methoxy-3- aminobenzoic acid amide, 4-methoxy-3-aminobenzoic acid anilide, 4-methoxy-3-aminobenzoic acid-3'-chloroanilide, 4- methoxy-B-aminobenzoic acid-2',5 '-dichloroanilide, 4- methoxy-3-aminobenzoic acid-2' ,4 ,5 -trichloroanilide, 4-car bomethoxy-3-aminobenzoic acid anilide, 4-methoxy-3- aminobenzoic acid-3'trifluoromethylanilide, 4-carbethoxy-3- aminobenzoic acid-2' ,5 dichloroanilide, 4-methoxy-3 aminobenzoic acid-3 ,5 -bis-trifluoromethylanilide, 4- methoxy-3-aminobenzoic acid-2-chloro-5 trifluorornethylanilide, 4-methoxy-3-aminobenzoic acid-2 ,5 dimethoxy-4'-chloroanilide and 4-methoxy-3-aminobenzoic acid-2 ,5 -dimethyl-4-chloroanilide.

The azo dyestuff carboxylic acids thus obtained are treated with substances which are capable of converting carboxylic acids into their halides, for example, their chlorides or bromides, such substances being, in particular, phosphorus halides, for example, phosphorus pentabrornide, phosphorus trichloride or phosphorus pentachloride, phosphorus oxyhalides and preferably thionyl chloride.

The treatment with the said acid halogenating agents is advantageously carried out in an inert organic solvent, for example, dimethylformarnide. a chlorobenzene, for example. monochlorobenzene or dichlorobenzene, toluene, xylene, or nitrobenzenev If desired, dimethylformamide may be used in conjunction with the last five solvents specified.

When preparing the carboxylic acid halides, it is generally advantageous first to dry the azo compounds which are prepared in an aqueous medium. or to free them from water by azeotropic distillation in an organic solvent. if desired, azeotropic drying may be carried out immediately prior to the treatment with the acid halogenating agents.

The azo dyestuff carboxylic acid chlorides so obtained are then condensed with an aminophenomorpholone-( 3). preferably a 7-aminophenomorpholone-( 3 of the formula in which Z represents a hydrogen or a halogen atom or an alkyl or alkoxy The following are given as examples of aminophenomorpholones-( 3 7-aminophenomorpholone-( 3 7-amino-6- 7-amino-6-methox- 7-amino-6-chlorophenoand 6- tained by condensing an azo dyestuff carboxylic acid chloride of the formula y MON li- R1 (1m with an aminobenzene or an aminophenomorpholone-(3l. and the pigments of formula (6) may be obtained by condensing an azo dyestuff carboxylic acid chloride of the formula with an ammobenzene or an aminophenomorpholone-i I The azo dyestuff carboxylic acids from which the azr dyestuff carboxylic acid chlorides of formula l l l are derived may be obtained by coupling a diazo compound of an aminobenzoic acid of the formula for example of 3-amino-4-chloro-. 3-amino-4-methylor amino 4-methoxy-benzoic acid, with the corresponding acetoacetylaminophenomorpholone.

Condensation between the carboxylic acid halides of the kind defined above the the aminophenomorpholone-l3l or aminobenzene is advantageously carried out in an anhydrous medium Under these conditions it generally proceeds surprisingly easily. even at temperatures within the boiling range of the common organit solvents, for example. toluene. monochlorobenzene. dichlorobenzene. trichlorobenzene. nitrobenzene and the like To accelerate the reaction. it is generally advantageous to use an agent capable of binding acid. for example. anhydrous sodium acetate or pyridine, Some of the products obtained are crystalline and some are amorphous and they are generally obtained in a very good yield and in a pure state It is expedient first to isolate the acid chlorides obtained from the carboxylic acids In some cases. however isolation of the acid chlorides may be omitted without harm and condensation may be carried out immediately after preparation of the carboxylic acid chlorides The pigments of the formula (2) may also be obtained by coupling a diazt u impound of an aminobenzene of the formula li -NH; with a naphthol of the formula The pigments of the formula (5) may also advantageously be obtained by coupling a diazotized aminophenomorpholone with the corresponding acetoacetylaminophenomorpholone Finally. the pigments of the formula (8) are also best obtained by a coupling process. namely by coupling a diazotized arylenediamine with the corresponding acetoacetylaminophenomorpholone. and the pigments of for mula (7) may be obtained by coupling a diazotized aminophenomorpholone-fli with a bisacetoacetyla rylenediamme in a molar ratio of 2 l Coupling is advantageously effected by gradual addition of the aqueous alkaline solution of the coupling component to the acidic solution of the diazonium salt. The alkali metal hydroxide used t dissolve the coupling component is advantageously used in an amount such that there is sufficient present to neutralize the mineral acid liberated from the diazonium salt during coupling Coupling is advantageously carried out at a pH value of 4 to 6 The pH value is advantageously adjusted by the addition of a buffer Suitable buffers are. for example, the salts. especially the alkali metal salts. of formic acid. phosphoric acid or especially acetic acid. The alkaline solution of the coupling component advantageously contains a wetting agent. a dispersing agent or an emulsifying agent. for example. an aralkylsulphonate. for example. dodecylbenzenesulphonate ll the sodium salt of 1,1- naphtylmethanesulphonic acid. polycondensation products of alkylene oxides, for example. the product obtained by reacting ethylene oxide with paratertiary-octvtphenol. and also the alkylesters of sulphoricinoleates. for example n-butylsulphoricinoleate The dispersion of the \iiupllng component may also advantageously contain protective colloids for example, methylcellulose or small amounts of inert rganic solvents which are sparingly soluble or insoluble in water. for example, aromatic hydrocarbons which may be halogenated or nitrated, for example. benzene. toluene. x lene chlorobenzene. dichlorobenzenes or nitrobenzene. as well as aliphatic halogenated hydrocarbons. for example. carbon tetrachloride or trichloroethylene; also suitable are organic solvents miscible with water. for example acetone ethylene glycol monomethylether. methylethylketone. methanol. ethanol. isopropanol or dimethylformamide Coupling may also be carried out advantageously by continuously combining an acidic solution of the diazonium salt with an alkaline solution of the coupling component in a mixing nozzle whereby coupling takes place instantaneously Care must be taken to ensure that diazo component and coupling component are present in the mixing nozzle m equimolecular amounts. but it may be advantageous to use a small excess of coupling component. The simplest way oi doing this is by control of the pH value of the liquid in the mixing nozzle. Care must also be taken to ensure that the two solutions are in a state of violent turbulence in the mixing nozzle The pigment dispersion formed is removed continuouslx from the mixing nozzle and the pigment is isolated by filtration In process (c) of the invention. the new pigments may be obtained by heating a diazoamino compound containing the residue R together with the coupling component in an organit solvent or in an aqueous organic sol ent. preferably in the presence of an acid The aryldiazoamino compounds to be used in accordance with the invention may he obtained by a known process by condensing an aryldiazonium salt with a primary amine or preferably with a secondary amine A verv wide variety of amines are suitable for this purpose. for example aliphatic amines. for example. methylamine. ethylamine ethanolamine. propylamine. butylamine. hexylamine and especially dimethylamine. diethylamine diethanolamine. methylethanolamine. dipropylamine or dibutylamine, aminoacetic acid. rnethylaminoacetic acid. butvlaminoacetic acid. aminoet'nane sulfonic acid. methylaminoethanesulphonic and. guanvlethane sulfonic acid B-aminoethyl sulfuric acid BllCyCllt. amines for example. cyclohexylamine. N-methycvclohexylamine, dicyclohexylamine; aromatic amines. for example 4-aminobenzoic acid. sulfanilic acid. -sulpho-Z-ammobenzotc acid 4-sulphophenyI i-guanidine. 4-N-methylaminobenzoit acid 4- ethylaminobenzoic acid. l-aminonaphthalene 4sulfonit acid. I ammonaphthalenel.4-disulphonic acid heterocyclic amines. for example. piperidme. morpholine. pyrrolidine, dihydroindol. and also sodium cyanamide or dicycanodiamide Generally. the diazoammo compounds obtained are sparingly soluble in cold water and. if necessary may be separated from the eaction medium in a crystalline form by salting out ln many cases. the moist-press cake may be used as it is for further reactions. in some cases. it may be advantageous to dehydrate the diazoamino compounds by vacuum drying prior to the reaction.

Coupling of the diazoamino compound with the naphthol may be carried out in an organic solvent. for example, chlorobenzene, ortho-dichlorobenzene nitrobenzene, pyridine, ethylene glycol, ethylene glycol monomethylether or ethylene glycol monoethylether. dimethylformamide. formic acid or acetic acid. When using a solvent which 15 miscible with water, it is not necessary to use the diazoamino compound in an anhydrous form. For example, the water-moist filter cake may be used. Splitting of the diazoamino compound which precedes coupling is carried out in an acid medium. When a neutral solvent is used, it is necessary to add an acid, for example, hydrochloric acid, sulfuric acid, formic acid or acetic acid.

Coupling is advantageously carried out with the application of heat, preferably at a temperature within the range of from 80 to 180 C., and it generally proceeds quickly and is complete.

By virtue of their insolubility, the pigments obtained may be isolated from the reaction mixture by filtration. Since the byproducts remain in solution, the pigments are obtained in a very pure state. Pigments that have been obtained by coupling in an aqueous medium are advantageously subjected to an aftertreatment with an organic solvent. Further advantages of the processes of the invention are the high yield, the production of the pigments in a form suitable for use and the constant properties of the pigments obtained.

By virtue of their advantageous properties, the pigments obtained in accordance with the processes of the invention may be used for a very wide variety of purposes. For example, they may be used in a finely divided form for the coloration of material of high molecular weight, for example, cellulose ethers and esters, polyamides, polyurethanes and polyesters, lacquers and lake-formers, solutions or products made from cellulose acetate, nitrocellulose, natural or synthetic resins, for example, polymerization resins or condensation resins, for example, aminoplasts, alkyd resins, and phenoplasts, and also polyolefines, for example, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyacrylonitrile, rubber, casein, silicones and silicon resins. They may also be used advantageously in the manufacture of colored pencils, cosmetic preparations and laminated sheet material.

The following examples illustrate the invention. Unless otherwise stated, the parts and percentages are by weight.

EXAMPLE 1 3.9 Parts by volume of dimethylformamide and 7.l parts by volume of thionyl chloride are added to 27.4 parts of the dyestuff obtained by coupling diazoitized l-(3-amino-4'- chlorobenzoylamino )-2-chloro-5-trifl uoromethylbenzene with 2,3-hydroxynaphthoic acid in 250 parts by volume of chlorobenzene. The mixture is heated for 12 hours at to C. and then allowed to cool. The crystalline dyestuff acid chloride is isolated by filtration, washed with a smail amount of benzene and dried in vacuo at 60 to C. 23.] Parts of the chloride are obtained (81.6 percent of the theoretical yield).

l7.0 Parts of the chloride so obtained together with 5.57 parts of 7-aminophenornorpholone-(3) are heated for 12 hours at to C. in 1,300 parts by volume of chlorobenzene. The pigment which forms is then isolated by filtration while hot. washed with hot ortho diochlorobenzene. ethanol and water and then dried in vacuo at 60 to 70 C. 15.7 Parts (75.5 percent of the theoretical yield) of a brown powder are obtained. The pigment corresponds to the formula The following table lists further components from which pigments can be obtained in the manner described above. Column I lists the diazo base used, Column 11 the condensation base and Column Ill indicates the shade produced by the pigment in polyvinyi chloride film.

I II III 1-(3-amin0-4'-ch1or0benzoylamino)2,5-dich10r0benzene Yellow-brown.

. 1-(3-amin04-chlorobenzoylamino)-benzene o Red-brown.

, 1-(3-amino 4'-chlorobenzoylamino)-2,5-dichl0robenzenc 6-meth0xy-7-aminophcnomorpholone-(S) Brown. 1-(3-amin0-4-mcthylb0nzoylamino)-3 trifluoromethylbenzcne T-aminqphcnomorphclone-(8 Scarlet.

. 1-(3'-arninot-clilorobenzoylamlno)-2-chloro-5 triiluoromethylbenzene d0. Brown.

. 3-aminoi-chlorobcnzoic acid phcnylamido .do ed.

. 1-(3'-arnlno-4'-chlorobenzoylamino)-2-triflu0r0metliyl-4-chlorobc .d0 Orange t-amino-2-methoxy4-chiorobenzene ...do Red.

3-amino-4chl0rO-bcnz0ic acid phenylamide. .do Reddish orange.

. 1-(3'amima ehlorobenzoylamino)-2,4,5-tricl1l01c cnzcne do Brownish orange- 1-amino-2,4,5-trichlorobcnzenc 1nmino-2-chloro-5-trilluorom ethylbenzene 1-(3-aminoAmhlorobcnzoylamina)-2,4dichlprobenzenc .do l-(3-aminochlorobonzoylamino)-2-triflu0romethyl-4-ch1orobonzenc .do 1-(3-mnino-4-m ethylbonzoylamlno) -2,4-dichlorobenzenc d0 l-(3'-:uninobenzoylamino)-2-ch1oro-5-trifluoromcthylbenzcnc .do

Ycilowislt brown. Brown. Brownish rod. Scarlet.

Red.

Ruby.

. Yellowish brown. Scarlet.

Reddish orange. D0.

. Claret. Scarlet.

Brownish orange.

1 11 Ill 46. 1-(3-nmino-4-motliylbuuzoylimilno)-2-meth0xybunzone r .d0... s m- 47.. 1-(3-mnino-4-methylbenzoylumino)-2-nicthylbcnzme ML 48 l-(3-aniiuo4-methylbenzoylnmino)-2-chlorobenzeno o Rod. 49.. l-(3-amino4-chlorobenzoylamlno)-2,4-dichlorobenzene.... fiamlno-E-ehlorophenomorpliolone-(3). R L 50 l-g3-amino-4 meth0xybenzoylamino)-2ohlorobenzen0 7amin0-phenomorpliolone-(3) Blulsh-rod, 51.. tl chloro-7-aminophenomorpholone-(B) 6-eh10r0-7amln0phenomorpholone-(3) el 52.. l-amino-2-chloro-4-methylbenzene... scarlet. 53.. l-aminc-2,5-dichlol0benzene -methoxy-7-amm0phenomorpholone-(B) Y u w br 54... 1-(3amino y-chlorobenzoylamino)-2-trifl110r0methyl-l-chlorobenlene.- 0 D 55.. 3chloro-l-aminophenylmethylsulphone fi-methyl-7-aminophenomorpholone-(3) Do, 56.. 1-(3-amlnobenzoylamino)-2-chloro-5-trifiuoromethylbenzene.. .d0 Do. 57.. 1-(3-aminn-4'-methoxybenzoylamino)-benzene Red. 58.. .d 6-chl0r0-7-aminophen0;n0rpholono-(3) Red, 5 6-rnethoxy-7-amlnophenomorpholone-(3) Scarlet G0 G-amlno-phenomorpholone-(3) R b 61 fi-arnino-8-chlor0phonomorpholonc-(ii) Do. 62. ethoxy am uoro en 6-metl1yl-7-amlnophenomorpholonc-(B) Scarlet. 63. do 6-chl0ro-7-aminophenomorpholone-(3) Do. 64 1-(3-amin0-4-Inethylbonzoylamino)-3-trlflu0r0mothylbonzono. G-amlno-S-chlorophenomorpholonn-(Ii). Red. 65 .(lo 6chloro-7-aminophenomorpholonc-(s) Scarlet,

6-moth0xy-7-amlnophenomorpholono(3) Ruddish orange.

. Scarlet.

. I: 6-methyl-7-amlnophcnomorpholonc-(Ii) EXAMPLE 2 A mixture comprising 37.05 parts of the dyestuff obtained by coupling diazoitized 3-amino-4-chlorobenzene-l-carboxylic acid with 2,3-hydroxynaphthoic acid, 150 parts by volume of chlorobenzene, 1.6 parts by volume of dimethylformamide and 16.5 parts by volume of thionyl chloride is heated for 3 hours at 70 to 75 C. and then allowed to cool. The dyestuff acid chloride in the form of coarse crystals is isolated by filtration and dried. 38 Parts of the acid chloride are obtained.

8.15 Parts of the acid chloride so obtained, together with 8.8 parts of 6-amino-8-chlorophenomorpholone-(3) and 3.2 parts by volume of pyridine, are heated for 12 hours at 130 to 140 C. in 500 pans by volume of chlorobenzene. The pigment which forms is isolated by filtration while hot and washed with hot chlorobenzene, hot alcohol and water. After drying in vacuo at 60 to 70 C., 13.1 parts of the pigment are obtained in the form of a dark red powder. When incorporated in polyvinyl chloride film in a finely divided form it produces a bloomy, red coloration which is fast to migration. The pigment corresponds to the formula A brown pigment may be obtained by replacing the 6- aminoS-chlorophenomorpholone-(3) mentioned in the second paragraph above with 6-methoxy-7- aminophenomorpholone-( 3 Example 3 0.8 Part by volume of dimethylformamide and 14.2 parts by volume of thionyl chloride are added to 51 parts of the dyestuff obtained by coupling diazotized 3-amino-4- chlorobenzene-l-carboxylic acid with l-(2,3'-hydroxynaphthoylamino)'2-methoxy-5-chlorobenzene, in 350 parts by volume of chlorobenzene. The mixture is heated to 130 to 140 C. and then minutes later a further 0.4 part by volume of dimethylformamide and 7.2 parts by volume of thionyl chloride are added. After a further 30 minutes, the batch is allowed to cool and the crystallized dyestuff acid chloride is isolated in the usual manner. 50.7 Parts of the acid chloride are obtained.

5.3 Parts of the acid chloride so obtained, together with 2.1 parts of 6-amino 8-chlorophenomorpholone-(3) and 0.8 part by volumgf pyridine, are heated for 12 hours at 130 to 140 A very similar result may be obtained by replacing the 6- amino-8-chlorophenomorpholone-( 3) mentioned in the second paragraph above with 6-methyl-7- aminophenomorpholone-( 3 6-methoxy-7- aminophenomorpholone-(3) leads to the production of an orange shade.

Example 4 2.95 Parts of l-(3'-amino-4-chlorobenzoylamino)-2- methyl-S-chlorobenzene are dissolved in 10 parts by volume of glacial acetic acid with 3 parts by volume of concentrated hydrochloric acid and then diazotized at 0 to 5 C. with 5 parts by volume of 2N sodium nitrite. The batch is stirred for 30 minutes, diluted with an equal volume of ice water, and then the diazo solution is run during 15 minutes into a solution of 3.35 parts of 7-(2',3'-hydroxynaphthoylamino)- phenomorphol one-(3) in parts by volume of dimethylformamide to which 2 parts of anhydrous sodium acetate have been added. Coupling takes place instantaneously. After 2 hours, the pigment is isolated by filtration, washed with dimethylformamide, water and methanol and then dried. 5.8 Parts of thepigment of the formula are obtained. When converted into a state of fine division by one of the usual methods, the pigment imparts to polyvinyl chloride a dull red shade that is fast to migration.

The 7-(2',3'-hydroxynaphthoylamino)-phenomorpholone- (3) may be obtained by condensing 2,3-hydroxynaphthoic acid with 7-aminophenomorpholone-(3) in toluene with phosphorus trichloride as condensing agent. it has a melting point above 300 C.

Example 5 2l .6 Parts of the azo dyestuff carboxylic acid obtained by coupling diazotized 3-amino-4-chlorobenzene-l-carboxylic acid with 7-acetoacetylaminophenomorpholone-(3) in a medium acidified with acetic acid, together with 0.4 part by volume of dimethylformamide and 7.1 parts by volume of thionyl chloride, are heated for 3% hours at 65 to 70 C. in 250 parts by volume of chlorobenzene. A suspension of fine crystals in the form of needles is formed. After cooling, the batch is filtered and the filter residue is dried in vacuo at 50 to 60 C. 21.8 Parts of the azo dyestufi carboxylic acid chloride are obtained.

4.5 Parts of the acid chloride so obtained are heated for 12 hours at 130 to 140 C. in 150 parts by volume of orthodichlorobenzene in admixture with 1.7 parts of l-amino- 2,5-dichlorobenzene. After this period the pigment which forms is isolated by filtration while hot, washed successively with hot ortho-dichlorobenzene, dimethylformamide, methanol and water and then dried. 3.5 Parts of a greenish yellow pigment powder are obtained which colors polyvinyl chloride a greenish yellow shade which is fast to migration. The pigment probably corresponds to the following formula 1 Aminobcnzcnc tiroonisli yellow. 2 laim1n0-2,5 licl|lnrobenzenc Do. 3. I'ktIlllilo-2,5-(llclll0l'0-4-bfillZOYiilflllllOhtlllZCllU. Yellow. l.. lchloroJ-amiiioplicnomotplwhine-t3) Urueuisli yellow.

The acetoacetylaminophenomorpholones-(3) used in this and the following examples may easily be obtained by reacting the appropriate aminophenomorpholones-(li) with diketene in an acetic acid medium. They have the following melting points:

2H) 2ll"( 7-2icctoacetylamino-b-methoxyphenomorpholonc- [3) ti-ucetoucetyliinii nob-chlorophenomorpholone l 3) EXAMPLE6 3.26 Parts of 3,3'-dichloro-4,4-diaminodiphenyl dihydrochloride are stirred for 2 hours in 20 parts by volume of water together with 5 parts by volume of concentrated hydrochloric acid. A small amount of ice is added and then 5 parts by volume of a 4N sodium nitrite solution are added dropwise to 0 to 5 C. within 30 minutes. The batch is stirred for l hour at 0 to 5 C. and then the tetrazo solution is clarified by filtration. This solution is then run at 10 to 15 C. within 15 minutes to a solution of 5 parts of 7- acetoacetylaminophenom0rpholone-(3) in 60 parts by volume of dimethylformamide to which 6.55 parts of anhydrous sodium acetate have been added. The coupling mixture is stirred overnight, the pigment which forms is isolated by filtration and then washed with water and alcohol and dried. 7.7 Parts of a brown, hard product are obtained which may converted into a state of fine division by one of the usual methods. It then colors polyvinyl chloride a strong, orange shade which is fast to migration. The pigment corresponds to the formula 1.78 Parts of 6-methyl-7-aminophenomorpholone-(3) are stirred in 10 parts by volume of water together with 2.5 parts by volume of concentrated hydrochloric acid. The batch is cooled to 0 C. by external cooling, 10 parts of ice are added, and diazotization is effected within 5 to l0 minutes by the dropwise addition of 5 parts by volume of a 2N sodium nitrite solution. The batch is stirred for 30 minutes, a small amount of sulfamic acid is added to destroy any small excess of sodium nitrite that may be present, and then small amounts of impurities are removed by filtration. This solution is run into a mixture of 2.62 parts of a 6-methyl'7-acetoacetylamino phenomorpholone-( 3 50 parts by volume of dimethylformamide and 3.3 parts of anhydrous sodium acetate within half an hour. The batch is stirred for several hours at room tempera ture and then the pigment that forms is isolated by filtration, washed with water and menthanol and dried. To convert the pigment into a form suitable for coloristic purposes, it is pul' verized and heated from to C. within 30 minutes in 75 parts by volume of dimethylsulphoxide. After cooling, the recrystallized pigment is isolated by filtration, washed with water and methanol and dried. 4.3 Parts of a bright yellow powder are obtained which colors polyvinyl chloride a strong yellow shade possessing good fastness to migration and light. The pigment corresponds to the formula The following table lists further components from which pigments may be obtained by the process described above. Column 1 lists the diazo component, column ll the coupling component and column III the shade produced with the pig ment in polyvinyl chloride.

wherein Z is hydrogen, chlorine, lower alkyl or lower alkoxy at least one of R and R being a phenomorpholine-(3) radical; R is selected from the group consisting of a group of the formula ll III I 6-Inethoxy-7-aminophenomorpholone-(3) 6-methoxy-7-acetoacetylamino phenomorhpnlono-(is) Yellow. 2 .do. 7-ocetoacetylaminophenomorpholone-(3) Do. 3 do. 6-methyl-7-acetoacetylaminophenomorpholone-(3) Orange. 4 ti-chloro-7-aminophenomorpholone-(Zi) 7-acetoacetylaminophenomorpholone-(3) Gruenish yellow 5 6-methyI-7-aeetoncetylnrnlnophenomorpholone-(li) Yellow. 6 do fichloro-7-acetoacetylaminoplrenomorpholone-(S) Greenlsh yellon 7 6-methyl-7-amonophenomorpholone-(3)H do Orange. 8 7-acetoacetylamin0phenomorpholone-(S) Yellow. 5! 7-amino-phenomorpholone-(3) 6-methy1-7-ucetoacetylaminophenomorpholone-(3) Do. 10 .do 7-ucetoacetylmninophenomorpholone-(3) (lrcenlsh yellow. 11 l-(3-amino-t-ehlorobenzoylamino)-2-chloro-5-trlfluoro- 6chloro-7-acetoaeetylnniinophenomorpholone-(3). Do.

methylbenzene. l2 6-methyl-7-amlnophenomorphclone-(3).. S-acetoacetylamlnoben211nldazolone Brown. 13. fi-meth02iy-7-aminophenomorphclone-(3) .4-acetonacetylantinonaphthostyril. Yellow. 14 .do 6-0hloro-7-acetoncetylamii10phenomorpholone-(3) Orange. 15 .do 5-acetoacetylaminobclizirnidazolone Yellow. 16. T-amino-phenomorpholone-(3) .4-ucetoacetyliirnlnonaphthostyriL Im. 17 6-chloroJacetoacetylaml11ophenomorpholone-(3) (lreenlshyellow l8 do G-methoxy-7-acetoacetylaininophenomorpholone-(3) Do. 19 do 5-acetoacetylaminobeltzintidazolone D0. 20 6-chloro-7-aminophenomorpholone-(3) 4-acet0acetylornlnonaplitItostyril lirownlshornnge. 21. o 6-meth0xy-7-acetoacetylatninophenornorpholone-(3) Y low. 22. ..do 7-(2,3hydroxynapthoylamlno)-phenomorpholone-(3) Maroon.

EXAMPLE 8 wherein V represents hydrogen, chlorine, trifluorornethyl, carboxylic amide group selected from the group consisting of CONl-l-aryl, wherein aryl is benzene, naphthalene or paradiphenyl or benzene, naphthalene or para-diphenyl substituted with chloro, lower alkyl, lower alkoxy or trifluoromethyl, or phenomorpholine-(3) group of the formula wherein Z is selected from the group consisting of hydrogen, chloro, lower alkyl or lower alkoxy; X is hydrogen, chlorine, lower alkyl, lower alkoxy, phenoxy, chlorophenoxy, lower alkylphenoxy, nitro or carbomethoxy; U is hydrogen, chlorine, nitro or trifluoromethyl; and phenomorpholine-(3) radical of the radical COCH;

l and -011.

wherein N N is attached to the one position of the above formula and Y is hydrogen, bromine, methoxy and cyano: and a pigment of the formula 0C COCH:

and Y, is hydrogen, chlorine, lower alkyl or lower alkoxy.

2. A monoazo pigment as claimed in claim 1 of the formula on O\ o H E 0N Y c o N/ Z I in which X represents hydrogen, chlorine, lower alkyl, lower alkoxy, phenoxy, chlorophenoxy, lower alkylphenoxy, nitro or carbomethoxy, U represents hydrogen, chlorine, nitro or trifluoromethyl, V Y represents hydrogen, chlorine,

trifluoromethyl or, carboxylic amide group selected from the S. A monoazo pigment as claimed in claim 1 of the formula group consisting of -CONH-aryl, wherein aryl is benzene, naphthalene or para-diphenyl or benzene, naphthalene or 0 para-diphenyl substituted with chloro, lower alkyl, lower al- 30011, m koxy or trifluoromethyl; and aphenomorpholine-(IJ) group of 5 N=N--CHC ON I l the-formula 0 (l CH, in which Z represents hydrogen, chlorine lower alkyl or'lower 0 alkoxy. N/ 6. A monoazo pigment as claimed in claim 1 of the formula H n o 0 CH, /\NNC BH--C ONH E wherein Z is selected from the group consisting of hydrogen, C 0

chloro, lower alkyl or lower alkoxy, Z represents hydrogen,

chlorine, lower alkyl or lower alkoxy and Y is hydrogen,

bromine, methoxy or cyano. C ONH RG 3. A monoazo pigntent as claimed in claim 2 of the formula in which X, represents chlorine, lower alkyl or lower alk'oxy,

R represents benzene or substituted benzene wherein the sub- I stituent is chloro, lower alkyl, lower alkoxyor trifluoromethyl; or a phenomorpholone-( 3) group of the formula 1] l A-Aryl H I on,

C=O Z I t H V "-7 V H. w .1, wherein Z is selected from the group consisting of hydrogen, in whichX represents hydrogen, chlorine, lower alkyl or chloro, lower alkyl or lower alkoxy. lower alkoxy, A represnts -CONl-I- group situated in meta-pr I 7. A disazo pigment as claimed in claim 1 of the formula para-position to the amino group, aryl" representsbenzene, naphthylene or para-diphenyl, or substituted benzene,

naphthylene or para-diphenyl wherein the substitutent is Y, chlorine, lower alkyl, lower alkyxy or trifluoromethyl, Z is l chlorine, hydrogn, lower alkyl or lower alkoxy, and Y is H --NHCOCHN=N hydrogen, bromine, methoxy or cyano. I O CH 4. A monoazo pigment as claimed in claim 1 of the formula 0 J N 1!! Z X1 Y] N 0 t N=N(l3HCONH 1 CONE-R, (10cm Co OH N Z l H CONHR w in which X, represents chlorine, lower alkyl or lower alkoxy, in which Y represents hydrogen chlorine lower alky] or R6 R7 each lepresms benzene or substituted benzene lower alkoxy and Z represents hydrogen,chlorine, lower alkyl wherein the substituent IS chloro, lower alkyl, lower alkoxy or 0 or lower alkoxy trifiuommethyl; or a group of the 8. The compound as claimed in claim 1 of the formula mu a Cl l (13H: f? ('11 c 0 N/ c 0 NH-@ Z H OH m 0 c F; c 0-NHm wherein Z is selected from the group'consisting of hydrogen, i l chloro, lower alkyl or lower alkoxy, at least one of the radicals R and R being aphenomorgholone-QL V 7 5 H N a, w N

OH 10. The compound as claimed in claim 1 of the formula CONH I HQ i N 13. The compound as claimed I formula I CO NH IFQ H3C :0 N l I CF:

OH 11. The compound as claimed in claim 1 of the formula Q CONH- G1 I HKC" C1 14. The compound as claimed w formula O O CONH- E N N 3 din H H 12. The compound as claimed in claim I of the formula in claim 1 of the in claim I of the 73 33 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,609, 13 Dated September 28, 1971 Inventor(s) RUDOLF MORY It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

[- Column 13, lines 55 to 60, the right-hand side of the formula should read:

9 CO N/ H Column 1 line 30, the left-hand side of the formula should read:

(IJOCH3 Column 1%, line #7, the left-hand side of the formula should read:

Column 15, line 42, delete "alkyxy" and insert alkoxy Column 16, lines 25 to 35, insert the following Page 1 of 2.

mg UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTIQN 3,609,134 Dated September 28, 1971 Patent No.

Inventor (s) RUDOLF MORY It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

formula:

Column 17, line 1, insert 9. The compound as claimed in claim 1 of the formula Column 18, line t, delete "PAT. NO. 360913 4".

Signed and sealed this 25th day of July 1972.

(SEAL) Attest:

Attesting Officer Page 2 of 2. 

2. A monoazo pigment as claimed in claim 1 of the formula
 3. A monoazo pigment as claimed in claim 2 of the formula
 4. A monoazo pigment as claimed in claim 1 of the formula
 5. A monoazo pigment as claimed in claim 1 of the formula
 6. A monoazo pigment as claimed in claim 1 of the formula
 7. A disazo pigment as claimed in claim 1 of the formula
 8. The compound as claimed in claim 1 of the formula
 9. The compound as claim in claim 1 of the formula
 10. The compound as claimed in claim 1 of the formula
 11. The compound as claimed in claim 1 of the formula
 12. The compound as claimed in claim 1 of the formula
 13. The compound as claimed in claim 1 of the formula
 14. The compound as claimed in claim 1 of formula 